Adam A. E. Fouda
Improving the predictive quality of time‐dependent density functional theory calculations of the X‐ray emission spectroscopy of organic molecules
Fouda, Adam A. E.; Besley, Nicholas A.
Nicholas A. Besley
The simulation of x-ray emission spectra of organic molecules using time-dependent density functional theory (TDDFT) is explored. TDDFT calculations using standard hybrid exchange-correlation functionals in conjunction with large basis sets can predict accurate X-ray emission spectra provided an energy shift is applied to align the spectra with experiment. The relaxation of the orbitals in the intermediate state is an important factor, and neglect of this relaxation leads to considerably poorer predicted spectra. A short-range corrected functional is found to give emission energies that required a relatively small energy shift to align with experiment. However, increasing the amount of Hartree-Fock exchange in this functional to remove the need for any energy shift led to a deterioration in the quality of the calculated spectral proﬁle. To predict accurate spectra without reference to experimental measurements, we use the CAM-B3LYP functional with the energy scale determined with reference to a ∆self-consistent ﬁeld (SCF) calculation for the highest energy emission transition.
|Journal Article Type||Article|
|Publication Date||Apr 30, 2020|
|Journal||Journal of Computational Chemistry|
|Peer Reviewed||Peer Reviewed|
|APA6 Citation||Fouda, A. A. E., & Besley, N. A. (2020). Improving the predictive quality of time‐dependent density functional theory calculations of the X‐ray emission spectroscopy of organic molecules. Journal of Computational Chemistry, 41(11), 1081-1090. https://doi.org/10.1002/jcc.26153|
|Keywords||General Chemistry; Computational Mathematics|
|Additional Information||Received: 2019-10-15; Accepted: 2020-01-08; Published: 2020-01-22|
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